Compositions comprising pyridine carboxylate herbicides and azole carboxylate safeners

ABSTRACT

Disclosed herein are safened compositions comprising (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt or ester thereof and (b) an azole carboxylate safener or agriculturally acceptable salt or ester thereof. Also disclosed herein are methods of controlling undesirable vegetation, comprising applying to vegetation or an area adjacent the vegetation or applying in soil or water to control the emergence or growth of vegetation (a) a pyridine carboxylate herbicide or an agriculturally acceptable N-oxide, salt or ester thereof and (b) an azole carboxylate safener or agriculturally acceptable salt or ester thereof.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority of U.S. ProvisionalApplication No. 62/756,173, filed Nov. 6, 2018, which is incorporated byreference herein in its entirety.

FIELD OF THE DISCLOSURE

The disclosure includes safened compositions comprising a pyridinecarboxylate herbicide and an azole carboxylate safener, as well asmethods of controlling undesirable vegetation using the same.

BACKGROUND

Many recurring problems in agriculture involve controlling the growth ofundesirable vegetation that can, for instance, negatively affect thegrowth of desirable vegetation. To help control undesirable vegetation,researchers have produced a variety of chemicals and chemicalformulations effective in controlling such unwanted growth.

In some cases, although a herbicide may be effective in controllingundesirable vegetation, it may also have a phytotoxic effect on a cropand cause injury or even kill the crop. there exists a need for newherbicides combined with safeners that limit the phytotoxicity of theherbicidal active ingredient with desired crops.

SUMMARY

Disclosed herein are safened compositions that may be used as aherbicides, for example, in crops. The safened compositions may contain(a) a pyridine carboxylate herbicide or agriculturally acceptableN-oxide, salt, or ester thereof and (b) an azole carboxylate safener oran agriculturally acceptable salt or ester thereof. The weight ratio of(a) to (b) can be from 1:5 to 5:1 (e.g., from 1:3 to 3:1, or from 1:2 to2:1).

In some aspects, the safened composition comprises (a) a pyridinecarboxylate herbicide defined by Formula (I):

wherein:

R¹ is cyanomethyl or propargyl;

R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl,alkoxycarbonyl, or acyl;

R³, R^(3′), R^(3″), and R^(3′″) are independently hydrogen, halogen,C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and(b) an azole carboxylate safener, or an agriculturally acceptable saltor ester thereof.

In some aspects, the safened composition comprises:

(a) the pyridine carboxylate herbicide compound cyanomethyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate,referred to hereinafter as Compound A:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and(b) an azole carboxylate safener or an agriculturally acceptable salt orester thereof.

In some aspects, the safened composition comprises:

(a) the pyridine carboxylate herbicide compound propargyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate,referred to hereinafter as Compound B:

or an agriculturally acceptable N-oxide, salt, or ester thereof; and(b) an azole carboxylate safener or an agriculturally acceptable salt orester thereof.

In some aspects, the azole carboxylate safener can be selected from thegroup consisting of selected from the group consisting of fenchlorazole,flurazole, furilazole, isoxadifen, mefenpyr, agriculturally acceptablesalts or esters thereof, and combinations thereof.

In some aspects, the composition can further comprise an agriculturallyacceptable adjuvant or carrier, an additional pesticide, or combinationsthereof. In some aspects, the only active ingredients in the compositionare (a) and (b). In some aspects, the composition can be provided as aherbicidal concentrate.

Also disclosed herein are methods of controlling undesirable vegetation,comprising applying to vegetation, to an area adjacent the vegetation,or to soil or water to control the emergence or growth of vegetation, asafened composition comprising: (a) a pyridine carboxylate herbicide oran agriculturally acceptable N-oxide, salt, or ester thereof; and (b) anazole carboxylate safener or an agriculturally acceptable salt or esterthereof. In some aspects, (a) and (b) are applied simultaneously. Insome aspects, (a) and (b) are applied sequentially. In some aspects, (a)and (b) are applied pre-emergence of the undesirable vegetation. In someaspects, (a) is applied pre-emergently or post-emergently to theundesirable vegetation, and (b) is applied as seed treatment to thecrop. In some aspects, (a) and (b) are applied post-emergence of theundesirable vegetation. In some aspects, the undesirable vegetation isin cereals. In some aspects, the undesirable vegetation is in maize,wheat, barley, rice, sorghum, millet, or oats. In some aspects, theundesirable vegetation is in broadleaf crops. In some aspects, theundesirable vegetation is in canola, flax, sunflower, soy, or cotton.

In some cases, the pyridine carboxylate herbicide (a) can be applied inan amount of from 0.1 gram active ingredient per hectare (g ai/ha) to300 g ai/ha (e.g., from 30 g ai/ha to 40 g ai/ha). In some cases, theazole carboxylate safener (b) can be applied in an amount of from 1 gai/ha to 300 g ai/ha (e.g., from 30 g ai/ha to 40 g ai/ha). In somecases, (a) and (b) can be applied in a weight ratio of from 1:5 to 5:1(e.g., from 1:3 to 3:1, or from 1:2 to 2:1).

The description below sets forth details of one or more aspect of thepresent disclosure. Other features, objects, and advantages will beapparent from the description and from the claims.

DETAILED DESCRIPTION

The present disclosure includes safened compositions comprising: (a) apyridine carboxylate herbicide or an agriculturally acceptable N-oxide,salt, or ester thereof and (b) an azole carboxylate safener or anagriculturally acceptable salt or ester thereof. The present disclosurealso includes methods for controlling undesirable vegetation. In someaspects, the undesirable vegetation is in cereals. In some aspects, theundesirable vegetation is in maize, wheat, barley, rice, sorghum,millet, or oats. In some aspects, the undesirable vegetation is inbroadleaf crops. In some aspects, the undesirable vegetation is incanola, flax, sunflower, soy, or cotton.

I. Definitions

Terms used herein will have their customary meaning in the art unlessspecified otherwise. The singular forms “a,” and “the” include pluralreferences unless stated otherwise. To the extent that the term “or” isemployed (e.g., A or B) it is intended to mean “A or B or both.” If thisdisclosure intends to indicate “only A or B but not both” then the term“only A or B but not both” will be employed. Thus, use of the term “or”herein is the inclusive and not the exclusive use.

The chemical moieties mentioned when defining variable positions withinthe general formulae described herein (e.g., the term “alkyl”) arecollective terms for the individual substituents encompassed by thechemical moiety. The prefix C_(n)-C_(m) preceding a group or moietyindicates, in each case, the possible number of carbon atoms in thegroup or moiety that follows.

As used herein, the terms “herbicide” and “herbicidal active ingredient”may be understood to include an active ingredient that kills, controls,or otherwise adversely modifies the growth of vegetation, particularlyundesirable vegetation such as weed species, when applied in anappropriate amount.

As used herein, the term “herbicidal effect” may be understood toinclude an adversely modifying effect of an active ingredient onvegetation, including, for example, a deviation from natural growth ordevelopment, killing, regulation, desiccation, growth inhibition, growthreduction, and retardation. The term “herbicidal activity” refersgenerally to herbicidal effects of an active ingredient.

As used herein, “applying” a herbicide or herbicidal composition refersto delivering it directly to the targeted vegetation or to the locusthereof or to the area where control of undesirable vegetation isdesired. Methods of application include, but are not limited to,pre-emergently contacting soil or water, post-emergently contacting theundesirable vegetation, or contacting the area adjacent to theundesirable vegetation.

As used herein, the term “vegetation” can include, for instance, dormantseeds, germinating seeds, emerging seedlings, plants propagating fromvegetative propagules, immature vegetation, and established vegetation.

As used herein, the term “crop” refers to desired vegetation, forinstance, plants that are grown to provide food, shelter, pasture,erosion control, etc. Example crops include cereals, legumes,vegetables, turf, grasslands, orchard and timber trees, grapevines, etc.Preferably, herbicides or herbicidal compositions have zero or minimalherbicidal effect on crops.

As used herein, the term “undesirable vegetation” refers to vegetationthat is not wanted in a given area, for instance, weed species.Herbicides or herbicidal compositions are used to control undesirablevegetation. Preferably, herbicides or herbicidal compositions have alarge or complete herbicidal effect on undesirable vegetation.

As used herein, “active ingredient” or “ai” may be understood to includea chemical compound or composition that has an effect on vegetation;specifically, a herbicidal effect or a safening effect on thevegetation.

As used herein, “acid equivalent” or “ae” may be understood to includethe amount of the acid form of an active ingredient that is calculatedfrom the amount of a salt or ester form of that active ingredient. Forexample, if the acid form of an active ingredient “Z” has a molecularweight of 100 Dalton, and the salt form of Z has a molecular weight of130 Dalton, an application of 130 g ai/ha of the Z salt would be equalto applying 100 g ae/ha of the acid form of Z:

130 g ai/ha Z salt*(100 Da Z acid/130 Da Z salt)=100 g ae/ha Z acid.

As used herein, unless otherwise specified, the term “acyl” may beunderstood to include a group of formula —C(O)R, where “C(O)” isshort-hand notation for C═O. In the acyl group, the R may be alkyl(e.g., C₁-C₆ alkyl), haloalkyl (e.g., C₁-C₆ haloalkyl), alkenyl (e.g.,C₂-C₆ alkenyl), haloalkenyl (e.g., C₂-C₆ haloalkenyl), alkynyl (e.g.,C₂-C₆ alkynyl), aryl or heteroaryl, or arylalkyl (e.g., C₇-C₁₀arylalkyl.

As used herein, the term “alkyl” may be understood to include saturated,straight-chained, branched, or cyclic saturated hydrocarbon moieties.Unless otherwise specified, C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆,or C₁-C₄) alkyl groups are intended. Examples of alkyl groups includemethyl, ethyl, propyl, cyclopropyl, 1-methyl-ethyl, butyl, cyclobutyl,1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl,cyclopentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl,2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, cyclohexyl,1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl,2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl,1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl,2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl,1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl,and 1-ethyl-2-methyl-propyl. Alkyl substituents may also be substitutedwith one or more chemical moieties. Examples of suitable substituentsinclude, for example, hydroxy, nitro, cyano, formyl, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₁-C₆ acyl, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆ haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆ alkoxycarbonyl, C₁-C₆ haloalkoxycarbonyl, C₁-C₆carbamoyl, C₁-C₆ halocarbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl,C₁-C₆ haloalkylcarbonyl, aminocarbonyl, C₁-C₆ alkylaminocarbonyl,haloalkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are stericallycompatible and the rules of chemical bonding and strain energy aresatisfied. Preferred substituents include cyano and C₁-C₆ alkoxy.

As used herein, the term “haloalkyl” may be understood to include alkylgroups wherein the hydrogen atoms may partially or entirely besubstituted with halogen atoms. Unless otherwise specified, C₁-C₂₀(e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl groups areintended. Examples include chloromethyl, bromomethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl,2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl.Haloalkyl substituents may also be substituted with one or more chemicalmoieties. Examples of suitable substituents include, for example,hydroxy, nitro, cyano, formyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆acyl, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆ haloalkoxycarbonyl, C₁-C₆ carbamoyl, C₁-C₆halocarbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl, C₁-C₆haloalkylcarbonyl, aminocarbonyl, C₁-C₆ alkylaminocarbonyl,haloalkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl, and C₁-C₆dihaloalkylaminocarbonyl, provided that the substituents are stericallycompatible and the rules of chemical bonding and strain energy aresatisfied. Preferred substituents include cyano and C₁-C₆ alkoxy.

As used herein, the term “alkoxy” may be understood to include a groupof the formula R—O—, where R is unsubstituted or substituted alkyl asdefined above. Unless otherwise specified, alkoxy groups wherein R is aC₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl group areintended. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy,butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy,pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy,2,2-dimethyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy,1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy,3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy,1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy,2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy,1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy,1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.

As used herein, the term “alkoxycarbonyl” may be understood to include agroup of the formula —C(O)OR, where R is an unsubstituted or substitutedalkyl as defined above. Unless otherwise specified, alkoxycarbonylgroups wherein R is a C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, orC₁-C₄) alkyl group are intended. Examples include methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, 1-methyl-ethoxycarbonyl,butoxycarbonyl, 1-methyl-propoxycarbonyl, 2-methyl-propoxycarbonyl,1,1-dimethyl-ethoxycarbonyl, pentoxycarbonyl, 1-methyl-butyloxycarbonyl,2-methyl-butoxycarbonyl, 3-methyl-butoxycarbonyl,2,2-dimethyl-propoxycarbonyl, 1-ethyl-propoxycarbonyl, hexoxycarbonyl,1,1-dimethyl-propoxycarbonyl, 1,2-dimethyl-propoxycarbonyl,1-methyl-pentoxycarbonyl, 2-methyl-pentoxycarbonyl,3-methyl-pentoxycarbonyl, 4-methyl-penoxycarbonyl,1,1-dimethyl-butoxycarbonyl, 1,2-dimethyl-butoxycarbonyl,1,3-dimethyl-butoxycarbonyl, 2,2-dimethyl-butoxycarbonyl,2,3-dimethyl-butoxycarbonyl, 3,3-dimethyl-butoxycarbonyl,1-ethyl-butoxycarbonyl, 2-ethylbutoxycarbonyl,1,1,2-trimethyl-propoxycarbonyl, 1,2,2-trimethyl-propoxycarbonyl,1-ethyl-1-methyl-propoxycarbonyl, and 1-ethyl-2-methyl-propoxycarbonyl.

As used herein, the term “haloalkoxy” may be understood to include agroup of the formula R—O—, where R is unsubstituted or substitutedhaloalkyl as defined above. Unless otherwise specified, haloalkoxygroups wherein R is a C₁-C₂₀ (e.g., C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, orC₁-C₄) alkyl group are intended. Examples include chloromethoxy,bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy,difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy,dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy,1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy.

As used herein, the term “aryl,” as well as derivative terms such asaryloxy, may be understood to include groups that include a monovalentaromatic carbocyclic group of from 6 to 14 carbon atoms. Aryl groups caninclude a single ring or multiple condensed rings. In some aspects, arylgroups include C₆-C₁₀ aryl groups. Examples of aryl groups include, butare not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl,phenylcyclopropyl, and indanyl. In some aspects, the aryl group can be aphenyl, indanyl or naphthyl group.

As used herein, the term “heteroaryl,” as well as derivative terms suchas “heteroaryloxy,” may be understood to include a 5- or 6-memberedaromatic ring containing one or more heteroatoms, for example, N, O orS. Heteroaryl rings may be fused to other aromatic systems. The aryl orheteroaryl substituents may also be substituted with one or morechemical moieties. Examples of suitable substituents include, forexample, hydroxy, nitro, cyano, formyl, C₁-C₆ alkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₁-C₆acyl, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆alkoxycarbonyl, C₁-C₆ carbamoyl, hydroxycarbonyl, C₁-C₆ alkylcarbonyl,aminocarbonyl, C₁-C₆ alkylaminocarbonyl, C₁-C₆ dialkylaminocarbonyl,provided that the substituents are sterically compatible and the rulesof chemical bonding and strain energy are satisfied. Preferredsubstituents include halogen, C₁-C₄ alkyl and C₁-C₄ haloalkyl.

As used herein, the term “halogen,” including derivative terms such as“halo,” refers to fluorine, chlorine, bromine and iodine.

As used herein, agriculturally acceptable salts and esters may beunderstood to include salts and esters that exhibit herbicidal activity,or that are or can be converted in plants, water, or soil to thereferenced herbicide. Exemplary agriculturally acceptable esters arethose that are or can be hydrolyzed, oxidized, metabolized, or otherwiseconverted, e.g., in plants, water, or soil, to the correspondingcarboxylic acid which, depending on the pH, may be in the dissociated orundissociated form.

Compounds described herein can include N-oxides. Pyridine N-oxides canbe obtained by oxidation of the corresponding pyridines. Suitableoxidation methods are described, for example, in Houben-Weyl, Methodender organischen Chemie [Methods in organic chemistry], expanded andsubsequent volumes to the 4th edition, volume E 7b, p. 565 f.

II. Pyridine Carboxylate Herbicides

Compositions and methods of the present disclosure include a safenedcomposition comprising (a) a pyridine carboxylate herbicide defined byFormula (I):

wherein:

R¹ is cyanomethyl or propargyl;

R² and R^(2′) are independently hydrogen, C₁-C₆ alkyl, formyl,alkoxycarbonyl, or acyl;

R³, R^(3′), R^(3″), and R^(3′″) are independently hydrogen, halogen,C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy;

or an agriculturally acceptable N-oxide, salt, or ester thereof; and(b) an azole carboxylate safener or an agriculturally acceptable salt orester thereof.

In some aspects, compositions and methods of the present disclosureinclude the safened composition comprising (a) the pyridine carboxylateherbicide cyanomethyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate,Compound A:

or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b)an azole carboxylate safener or an agriculturally acceptable salt orester thereof.

In some aspects, compositions and methods of the present disclosureinclude the safened composition comprising (a) the pyridine carboxylateherbicide propargyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate,Compound B:

or an agriculturally acceptable N-oxide, salt, or ester thereof, and (b)an azole carboxylate safener or an agriculturally acceptable salt orester thereof.

Pyridine carboxylate herbicides defined by Formula (I), as well asmethods of making these pyridine carboxylate herbicides, are disclosedin application PCT/US2018/031004, filed May 4, 2018, the entiredisclosure of which is hereby expressly incorporated by reference.

In some aspects, the pyridine carboxylate herbicide can be provided asan agriculturally acceptable salt. Exemplary agriculturally acceptablesalts of the pyridine carboxylate herbicides include, but are notlimited to: sodium salts; potassium salts; ammonium salts or substitutedammonium salts, in particular mono-, di- and tri-C₁-C₈-alkylammoniumsalts such as methyl ammonium, dimethylammonium and isopropylammonium;mono-, di- and tri-hydroxy-C₂-C₈-alkylammonium salts such ashydroxyethylammonium, di(hydroxyethyl)ammonium,tri(hydroxyethyl)ammonium, hydroxypropylammonium,di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts; olaminesalts; diglycolamine salts; choline salts; and quatemary ammonium saltssuch as those represented by the formula R⁹R¹⁰R¹¹R¹²N⁺ and wherein R⁹,R¹⁰, R¹¹ and R¹² (e.g., R⁹-R¹²) each independently can representhydrogen, C₁-C₁₀ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₁-C₈ alkoxy,C₁-C₈ alkylthio, or aryl groups, provided that R⁹-R¹² are stericallycompatible.

In some aspects, the pyridine carboxylate herbicide can be provided asan agriculturally acceptable ester. Exemplary agriculturally acceptableesters of the pyridine carboxylate herbicides include, but are notlimited to: methyl, ethyl, propyl, 1-methyl-ethyl, butyl,1-methyl-propyl, 2-methyl-propyl, pentyl, 1-methyl-butyl,2-methyl-butyl, 3-methyl-butyl, 1-ethyl-propyl, hexyl, 1-methyl-hexyl(mexyl), 2-ethylhexyl, heptyl, 1-methyl-heptyl (meptyl), octyl, isooctyl(isoctyl), butoxyethyl (butotyl), and benzyl.

The pyridine carboxylate herbicide, or an agriculturally acceptableN-oxide, salt, or ester thereof, can be applied to vegetation or an areaadjacent the vegetation or applied to soil or water to prevent theemergence or growth of vegetation in an amount sufficient to induce aherbicidal effect. In some aspects, the pyridine carboxylate herbicide,or an agriculturally acceptable N-oxide, salt, or ester thereof, isapplied to vegetation or an area adjacent the vegetation or applied tosoil or water to prevent the emergence or growth of vegetation in anamount of 0.1 grams acid equivalent per hectare (g ae/ha) or greater,such as 0.2 g ae/ha or greater, 0.3 g ae/ha or greater, 0.4 g ae/ha orgreater, 0.5 g ae/ha or greater, 0.6 g ae/ha or greater, 0.7 g ae/ha orgreater, 0.8 g ae/ha or greater, 0.9 g ae/ha or greater, 1 g ae/ha orgreater, 1.1 g ae/ha or greater, 1.2 g ae/ha or greater, 1.3 g ae/ha orgreater, 1.4 g ae/ha or greater, 1.5 g ae/ha or greater, 1.6 g ae/ha orgreater, 1.7 g ae/ha or greater, 1.8 g ae/ha or greater, 1.9 g ae/ha orgreater, 2 g ae/ha or greater, 2.25 g ae/ha or greater, 2.5 g ae/ha orgreater, 2.75 g ae/ha or greater, 3 g ae/ha or greater, 4 g ae/ha orgreater, 5 g ae/ha or greater, 6 g ae/ha or greater, 7 g ae/ha orgreater, 8 g ae/ha or greater, 9 g ae/ha or greater, 10 g ae/ha orgreater, 11 g ae/ha or greater, 12 g ae/ha or greater, 13 g ae/ha orgreater, 14 g ae/ha or greater, 15 g ae/ha or greater, 16 g ae/ha orgreater, 17 g ae/ha or greater, 18 g ae/ha or greater, 19 g ae/ha orgreater, 20 g ae/ha or greater, 22 g ae/ha or greater, 24 g ae/ha orgreater, 25 g ae/ha or greater, 26 g ae/ha or greater, 28 g ae/ha orgreater, 30 g ae/ha or greater, 32 g ae/ha or greater, 34 g ae/ha orgreater, 35 g ae/ha or greater, 36 g ae/ha or greater, 38 g ae/ha orgreater, 40 g ae/ha or greater, 42.5 g ae/ha or greater, 45 g ae/ha orgreater, 47.5 g ae/ha or greater, 50 g ae/ha or greater, 52.5 g ae/ha orgreater, 55 g ae/ha or greater, 57.5 g ae/ha or greater, 60 g ae/ha orgreater, 65 g ae/ha or greater, 70 g ae/ha or greater, 75 g ae/ha orgreater, 80 g ae/ha or greater, 85 g ae/ha or greater, 90 g ae/ha orgreater, 95 g ae/ha or greater, 100 g ae/ha or greater, 110 g ae/ha orgreater, 120 g ae/ha or greater, 130 g ae/ha or greater, 140 g ae/ha orgreater, 150 g ae/ha or greater, 160 g ae/ha or greater, 170 g ae/ha orgreater, 180 g ae/ha or greater, 190 g ae/ha or greater, 200 g ae/ha orgreater, 210 g ae/ha or greater, 220 g ae/ha or greater, 230 g ae/ha orgreater, 240 g ae/ha or greater, 250 g ae/ha or greater, 260 g ae/ha orgreater, 270 g ae/ha or greater, 280 g ae/ha or greater, or 290 g ae/haor greater; in an amount of 300 g ae/ha or less, such as 290 g ae/ha orless, 280 g ae/ha or less, 270 g ae/ha or less, 260 g ae/ha or less, 250g ae/ha or less, 240 g ae/ha or less, 230 g ae/ha or less, 220 g ae/haor less, 210 g ae/ha or less, 200 g ae/ha or less, 190 g ae/ha or less,180 g ae/ha or less, 170 g ae/ha or less, 160 g ae/ha or less, 150 gae/ha or less, 140 g ae/ha or less, 130 g ae/ha or less, 120 g ae/ha orless, 110 g ae/ha or less, 100 g ae/ha or less, 95 g ae/ha or less, 90 gae/ha or less, 85 g ae/ha or less, 80 g ae/ha or less, 75 g ae/ha orless, 70 g ae/ha or less, 65 g ae/ha or less, 60 g ae/ha or less, 57.5 gae/ha or less, 55 g ae/ha or less, 52.5 g ae/ha or less, 50 g ae/ha orless, 47.5 g ae/ha or less, 45 g ae/ha or less, 42.5 g ae/ha or less, 40g ae/ha or less, 38 g ae/ha or less, 36 g ae/ha or less, 35 g ae/ha orless, 34 g ae/ha or less, 32 g ae/ha or less, 30 g ae/ha or less, 28 gae/ha or less, 26 g ae/ha or less, 25 g ae/ha or less, 24 g ae/ha orless, 22 g ae/ha or less, 20 g ae/ha or less, 19 g ae/ha or less, 18 gae/ha or less, 17 g ae/ha or less, 16 g ae/ha or less, 15 g ae/ha orless, 14 g ae/ha or less, 13 g ae/ha or less, 12 g ae/ha or less, 11 gae/ha or less, 10 g ae/ha or less, 9 g ae/ha or less, 8 g ae/ha or less,7 g ae/ha or less, 6 g ae/ha or less, 5 g ae/ha or less, 4 g ae/ha orless, 3 g ae/ha or less, 2.75 g ae/ha or less, 2.5 g ae/ha or less, 2.25g ae/ha or less, 2 g ae/ha or less, 1.9 g ae/ha or less, 1.8 g ae/ha orless, 1.7 g ae/ha or less, 1.6 g ae/ha or less, 1.5 g ae/ha or less, 1.4g ae/ha or less, 1.3 g ae/ha or less, 1.2 g ae/ha or less, 1.1 g ae/haor less, 1 g ae/ha or less, 0.9 g ae/ha or less, 0.8 g ae/ha or less,0.7 g ae/ha or less, 0.6 g ae/ha or less, 0.5 g ae/ha or less, 0.4 gae/ha or less, 0.3 g ae/ha or less, or 0.2 g ae/ha or less; or in anamount within any range defined between any pair of the precedingvalues, such as from 0.1 g ae/ha to 300 g ae/ha, from 1 g ae/ha to 150 gae/ha, from 10 g ae/ha to 200 g ae/ha, from 25 g ae/ha to 75 g ae/ha, orfrom 40 g ae/ha to 100 g ae/ha.

III. Azole Carboxylate Safeners

In addition to the pyridine carboxylate herbicide, the compositions andmethods of the present disclosure can include an azole carboxylatesafener or an agriculturally acceptable salt or ester thereof. Herbicidesafeners are molecules used in combination with herbicides to make them“safer”—that is, to reduce the herbicidal effect of the herbicide oncrop plants and to improve selectivity between crops and the undesirablevegetation being targeted by the herbicide. Herbicide safeners can beused to pre-treat crop seeds prior to planting. Herbicide safeners mayalso be sprayed on plants as a mixture with the herbicide, or separatelyand sequentially with the herbicide.

Azoles are a class of five-membered nitrogen heterocyclic ring compoundscontaining at least one additional heteroatom (e.g., nitrogen, sulfur,or oxygen) within the heterocyclic ring. Examples of azoles include, forexample, pyrazoles, imidazoles, thiazoles, oxazoles, isoxazoles andtriazoles.

Azole carboxylate safeners are a class of safeners based oncarboxylate-substituted azole moieties. Examples of azole carboxylatesafeners include pyrazole carboxylate safeners, imidazole carboxylatesafeners, thiazole carboxylate safeners, oxazole carboxylate safeners,isoxazole carboxylate safeners, and triazole carboxylate safeners. Insome aspects, the composition can include an azole carboxylate safenerselected from the group consisting of fenchlorazole, flurazole,furilazole, isoxadifen, mefenpyr, agriculturally acceptable salts oresters thereof, or combinations thereof. In some aspects, the azolecarboxylate safener can include fenchlorazole-ethyl, isoxadifen-ethyl,mefenpyr-diethyl, or combinations thereof.

In some aspects, the azole carboxylate safener can comprisefenchlorazole, shown below, or an agriculturally acceptable salt orester thereof. Fenchlorazole's safening activity is described in ThePesticide Manual, Eighteenth Edition, 2016.

In some aspects, the fenchlorazole is provided as an agriculturallyacceptable salt or ester. An exemplary agriculturally acceptable esterof fenchlorazole is fenchlorazole-ethyl, shown below.

In some aspects, the azole carboxylate safener can comprise flurazole,shown below, or an agriculturally acceptable salt or ester thereof.Flurazole's safening activity is described in The Pesticide Manual,Eighteenth Edition, 2016.

In some aspects, the azole carboxylate safener can comprise furilazole,shown below, or an agriculturally acceptable salt or ester thereof.Furilazole's safening activity is described in The Pesticide Manual,Eighteenth Edition, 2016.

In some aspects, the azole carboxylate safener can comprise isoxadifen,shown below, or an agriculturally acceptable salt or ester thereof.Isoxadifen's safening activity is described in The Pesticide Manual,Eighteenth Edition, 2016.

In some aspects, the isoxadifen is provided as an agriculturallyacceptable salt or ester. An exemplary agriculturally acceptable esterof isoxadifen is isoxadifen-ethyl, shown below.

In some aspects, the azole carboxylate safener can comprise mefenpyr,shown below, or an agriculturally acceptable salt or ester thereof.Mefenpyr's safening activity is described in The Pesticide Manual,Eighteenth Edition, 2016.

In some aspects, the mefenpyr is provided as an agriculturallyacceptable salt or ester. An exemplary agriculturally acceptable esterof mefenpyr is mefenpyr-diethyl, shown below.

In some aspects, the azole carboxylate safener can be provided as anagriculturally acceptable ester. Suitable esters include, but are notlimited to, methyl, ethyl, isopropyl, butyl, hexyl, heptyl, isoheptyl,mexyl, isooctyl, 2-ethylhexyl and butoxyethyl esters, and aryl esterssuch as benzyl. Exemplary agriculturally acceptable esters of the azolecarboxylate safeners described herein include methyl, ethyl, and diethylesters.

In some aspects, the azole carboxylate safener can comprise anagriculturally acceptable salt of the azole carboxylate safener.Agriculturally acceptable salts of the azole carboxylate safenerinclude, for example sodium, potassium, ammonium, monoethanolammonium,diethanolammonium, triethanolammonium, monoisopropanolammonium,diisopropanolammonium, triisopropanolammonium, choline,N,N-dimethylethanolammonium, diethylammonium, dimethylammonium,trimethylammonium, triethylammonium, and isopropylammonium salts of theazole carboxylate safener.

An azole carboxylate safener, when applied in combination withherbicides, can be used to reduce phytotoxicity to crops such as wheat,barley, triticale, rye, teff, oats, maize, sorghum, millet, rice,millet, canola/oilseed rape, flax, soy, sunflower, sugar beet, cotton,sugarcane, and pasture grasses.

The azole carboxylate safener or an agriculturally acceptable salt orester thereof can be used in an amount sufficient to induce a safeningeffect. In some aspects, the azole carboxylate safener is selected fromthe group consisting of fenchlorazole, fenclorim, flurazole, furilazole,isoxadifen, mefenpyr, an agriculturally acceptable salt or esterthereof, or combinations thereof, and is applied to vegetation or anarea adjacent the vegetation or applied to soil or water in an amount of1 g active ingredient per hectare (ai/ha) or greater, such as 2 g ai/haor greater, 3 g ai/ha or greater, 4 g ai/ha or greater, 5 g ai/ha orgreater, 6 g ai/ha or greater, 7 g ai/ha or greater, 8 g ai/ha orgreater, 9 g ai/ha or greater, 10 g ai/ha or greater, 11 g ai/ha orgreater, 12 g ai/ha or greater, 13 g ai/ha or greater, 14 g ai/ha orgreater, 15 g ai/ha or greater, 16 g ai/ha or greater, 17 g ai/ha orgreater, 18 g ai/ha or greater, 19 g ai/ha or greater, 20 g ai/ha orgreater, 22 g ai/ha or greater, 24 g ai/ha or greater, 25 g ai/ha orgreater, 26 g ai/ha or greater, 28 g ai/ha or greater, 30 g ai/ha orgreater, 32 g ai/ha or greater, 34 g ai/ha or greater, 35 g ai/ha orgreater, 36 g ai/ha or greater, 38 g ai/ha or greater, 40 g ai/ha orgreater, 42.5 g ai/ha or greater, 45 g ai/ha or greater, 47.5 g ai/ha orgreater, 50 g ai/ha or greater, 52.5 g ai/ha or greater, 55 g ai/ha orgreater, 57.5 g ai/ha or greater, 60 g ai/ha or greater, 65 g ai/ha orgreater, 70 g ai/ha or greater, 75 g ai/ha or greater, 80 g ai/ha orgreater, 85 g ai/ha or greater, 90 g ai/ha or greater, 95 g ai/ha orgreater, 100 g ai/ha or greater, 110 g ai/ha or greater, 120 g ai/ha orgreater, 130 g ai/ha or greater, 140 g ai/ha or greater, 150 g ai/ha orgreater, 160 g ai/ha or greater, 170 g ai/ha or greater, 180 g ai/ha orgreater, 190 g ai/ha or greater, 200 g ai/ha or greater, 210 g ai/ha orgreater, 220 g ai/ha or greater, 230 g ai/ha or greater, 240 g ai/ha orgreater, 250 g ai/ha or greater, 260 g ai/ha or greater, 270 g ai/ha orgreater, 280 g ai/ha or greater, or 290 g ai/ha or greater; in an amountof 300 g ai/ha or less, such as 290 g ai/ha or less, 280 g ai/ha orless, 270 g ai/ha or less, 260 g a/ha or less, 250 g ai/ha or less, 240g ai/ha or less, 230 g ai/ha or less, 220 g ai/ha or less, 210 g ai/haor less, 200 g ai/ha or less, 190 g ai/ha or less, 180 g ai/ha or less,170 g ai/ha or less, 160 g ai/ha or less, 150 g ai/ha or less, 140 gai/ha or less, 130 g ai/ha or less, 120 g ai/ha or less, 110 g ai/ha orless, 100 g ai/ha or less, 95 g ai/ha or less, 90 g ai/ha or less, 85 gai/ha or less, 80 g ai/ha or less, 75 g ai/ha or less, 70 g ai/ha orless, 65 g ai/ha or less, 60 g ai/ha or less, 57.5 g ai/ha or less, 55 gai/ha or less, 52.5 g ai/ha or less, 50 g ai/ha or less, 47.5 g ai/ha orless, 45 g ai/ha or less, 42.5 g ai/ha or less, 40 g ai/ha or less, 38 gai/ha or less, 36 g ai/ha or less, 35 g ai/ha or less, 34 g ai/ha orless, 32 g ai/ha or less, 30 g ai/ha or less, 28 g ai/ha or less, 26 gai/ha or less, 25 g ai/ha or less, 24 g ai/ha or less, 22 g ai/ha orless, 20 g ai/ha or less, 19 g ai/ha or less, 18 g ai/ha or less, 17 gai/ha or less, 16 g ai/ha or less, 15 g ai/ha or less, 14 g ai/ha orless, 13 g ai/ha or less, 12 g ai/ha or less, 11 g ai/ha or less, 10 gai/ha or less, 9 g ai/ha or less, 8 g ai/ha or less, 7 g ai/ha or less,6 g ai/ha or less, 5 g ai/ha or less, 4 g ai/ha or less, 3 g ai/ha orless, or 2 g ai/ha or less; or in an amount within any range definedbetween any pair of the preceding values, such as from 1 g ai/ha to 300g ai/ha, from 5 g ai/ha to 150 g ai/ha, from 10 g ai/ha to 200 g ai/ha,from 20 g ai/ha to 75 g ai/ha, or from 40 g ai/ha to 100 g ai/ha.

IV. Safened Compositions

A safened composition comprising (a) a pyridine carboxylate herbicide oran agriculturally acceptable N-oxide, salt, or ester thereof may bemixed with or applied in combination with (b) an azole carboxylatesafener or an agriculturally acceptable salt or ester thereof.

In some aspects, (a) and (b) are used in an amount sufficient to inducean unexpectedly enhanced herbicidal effect (e.g., increased damage orinjury to undesirable vegetation) while still showing good cropcompatibility (e.g., no increased damage to crops or minimal increaseddamage or injury to crops) when compared to the individual applicationof the herbicidal compounds (a) or (b). In some aspects, the damage orinjury to undesirable vegetation caused by the safened compositions andmethods disclosed herein is evaluated using a scale from 0% to 100%,when compared with the untreated control vegetation, wherein 0%indicates no damage to the undesirable vegetation and 100% indicatescomplete destruction of the undesirable vegetation. Similarly, in someaspects, the damage or injury to the crop caused by the safenedcompositions and methods disclosed herein is evaluated using a scalefrom 0% to 100%, when compared with control crops treated with only theherbicide or the safener, wherein 0% indicates no damage to the crop and100% indicates complete destruction of the crop.

In some aspects, the joint action of (a) the pyridine carboxylateherbicide or an agriculturally acceptable N-oxide, salt, or esterthereof and (b) the azole carboxylate safener or an agriculturallyacceptable salt or ester thereof results in unexpectedly enhancedherbicidal effect against undesirable vegetation, even at applicationrates below those typically used for the herbicide to have a herbicidaleffect on its own. In some aspects, the compositions and methodsdisclosed herein can, based on the individual components, be used atlower application rates to achieve a herbicidal effect comparable to theeffect produced by the individual components at normal applicationrates. In some aspects, the joint action of (a) the pyridine carboxylateherbicide or an agriculturally acceptable N-oxide, salt, or esterthereof and (b) the azole carboxylate safener or an agriculturallyacceptable salt or ester thereof results in an unexpected protectiveeffect for desired crops against damage to the crops that might becaused by the herbicide alone.

In some aspects, the weight ratio of (a) the pyridine carboxylateherbicide or an agriculturally acceptable N-oxide, salt, or esterthereof (in g ae/ha) to (b) the azole carboxylate safener or anagriculturally acceptable salt or ester thereof (in g ai/ha) can be 1:5or more, such as 1:4.75 or more, 1:4.5 or more, 1:4.25 or more, 1:4 ormore, 1:3.75 or more, 1:3.5 or more, 1:3.25 or more, 1:3 or more, 1:2.75or more, 1:2.5 or more, 1:2.25 or more, 1:2 or more, 1:1.9 or more,1:1.8 or more, 1:1.7 or more, 1:1.6 or more, 1:1.5 or more, 1:1.4 ormore, 1:1.3 or more, 1:1.2 or more, 1:1.1 or more, 1:1 or more, 1.1:1 ormore, 1.2:1 or more, 1.3:1 or more, 1.4:1 or more, 1.5:1 or more, 1.6:1or more, 1.7:1 or more, 1.8:1 or more, 1.9:1 or more, 2:1 or more,2.25:1 or more, 2.5:1 or more, 2.75:1 or more, 3:1 or more, 3.25:1 ormore, 3.5:1 or more, 3.75:1 or more, 4:1 or more, 4.25:1 or more, 4.5:1or more, 4.75:1 or more, or 5:1 or more; the weight ratio of (a) to (b)can be 5:1 or less, such as 4.75:1 or less, 4.5:1 or less, 4.25:1 orless, 4:1 or less, 3.75:1 or less, 3.5:1 or less, 3.25:1 or less, 3:1 orless, 2.75:1 or less, 2.5:1 or less, 2.25:1 or less, 2:1 or less, 1.9:1or less, 1.8:1 or less, 1.7:1 or less, 1.6:1 or less, 1.5:1 or less,1.4:1 or less, 1.3:1 or less, 1.2:1 or less, 1.1:1 or less, 1:1 or less,1:1.1 or less, 1:1.2 or less, 1:1.3 or less, 1:1.4 or less, 1:1.5 orless, 1:1.6 or less, 1:1.7 or less, 1:1.8 or less, 1:1.9 or less, 1:2 orless, 1:2.25 or less, 1:2.5 or less, 1:2.75 or less, 1:3 or less, 1:3.25or less, 1:3.5 or less, 1:3.75 or less, 1:4 or less, 1:4.25 or less,1:4.5 or less, or 1:4.75 or less; or the weight ratio of (a) to (b) canrange from any of the minimum ratios to any of the maximum ratiosprovided above, such as from 1:5 to 5:1, from 1:2 to 5:1, from 1:1 to3:1, from 1:3 to 4:1, or from 1:1.5 to 3.5:1.

In some aspects, (a) and (b), independently, can be employed in a purityof from 90% to 100% (e.g., from 95% to 100%) according to nuclearmagnetic resonance (NMR) spectroscopy.

V. Formulations

The present disclosure also includes formulations of the compositionsand methods disclosed herein.

A. Additives

The compositions and methods disclosed herein can also be mixed with orapplied with an additive. In some aspects, the additive is addedsequentially. In some aspects, the additive is added simultaneously. Insome aspects, the additive is premixed with the pyridine carboxylateherbicide or agriculturally acceptable N-oxide, salt, or ester thereof.In some aspects, the additive is premixed with the azole carboxylatesafener or agriculturally acceptable salt or ester thereof.

1. Other Pesticides

Some aspects of the disclosed safened compositions disclosed includeadding one or more additional pesticide active ingredients to thesafened compositions. These pesticide active ingredients may include oneor more of an herbicide, an insecticide, a fungicide, a nematocide, amiticide, a arthropodicide, a bactericide, a plant growth regulator, orcombinations thereof that are compatible with the compositions of thepresent disclosure.

In some aspects, the additive is an additional herbicide. For example,the compositions described herein can be applied in conjunction with oneor more additional herbicides to control undesirable vegetation. Thecomposition can be formulated with the one or more additionalherbicides, tank mixed with the one or more additional herbicides, orapplied sequentially with the one or more additional herbicides.Exemplary additional herbicides include, but are not limited to: 4-CPA;4-CPB; 4-CPP; 2;4-D; 2;4-D choline salt; 2,4-D salts, esters and amines;2,4-DB; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP; 2,4-DP; 3,4-DP; 2,3,6-TBA;2,4,5-T; 2,4,5-TB; acetochlor; acifluorfen; aclonifen; acrolein;alachlor; allidochlor; alloxydim; allyl alcohol; alorac; ametridione;ametryne; amibuzin; amicarbazone; amidosulfuron; aminocyclopyrachlor;4-aminopicolinic acid based herbicides, such as halauxifen,halauxifen-methyl, florpyrauxifen, and those described in U.S. Pat. Nos.7,314,849 and 7,432,227 to Balko, et al.; aminopyralid;amiprofos-methyl; amitrole; ammonium sulfamate; anilofos; anisuron;asulam; atraton; atrazine; azafenidin; azimsulfuron; aziprotryne;barban; BCPC; beflubutamid; benazolin; bencarbazone; benfluralin;benfuresate; bensulide; bensulfuron; benthiocarb; bentazone; benzadox;benzfendizone; benzipram; benzobicyclon; benzofenap; benzofluor;benzoylprop; benzthiazuron; bialaphos; bicyclopyrone; bifenox;bilanafos; bispyribac; borax; bromacil; bromobonil; bromobutide;bromofenoxim; bromoxynil; brompyrazon; butachlor; butafenacil;butamifos; butenachlor; buthidazole; buthiuron; butralin; butroxydim;buturon; butylate; cacodylic acid; cafenstrole; calcium chlorate;calcium cyanamide; cambendichlor; carbasulam; carbetamide; carboxazole;chlorprocarb; carfentrazone-ethyl; CDEA; CEPC; chlomethoxyfen;chloramben; chloranocryl; chlorazifop; chlorazine; chlorobromuron;chlorbufam; chloreturon; chlorfenac; chlorfenprop; chlorflurazole;chlorflurenol; chloridazon; chlorimuron; chlornitrofen; chloropon;chlorotoluron; chloroxuron; chloroxynil; chlorpropham; chlorsulfuron;chlorthal; chlorthiamid; cinidon-ethyl; cinmethylin; cinosulfuron;cisanilide; clacyfos; clethodim; cliodinate; clodinafop-propargyl;clofop; clomazone; clomeprop; cloprop; cloproxydim; clopyralid;cloransulam-methyl; CMA; copper sulfate; CPMF; CPPC; credazine; cresol;cumyluron; cyanatryn; cyanazine; cycloate; cyclopyrimorate;cyclosulfamuron; cycloxydim; cycluron; cyhalofop-butyl; cyperquat;cyprazine; cyprazole; cypromid; daimuron; dalapon; dazomet; delachlor;desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichloralurea;dichlormate; dichlorprop; dichlorprop-P; diclofop-methyl; diclosulam;diethamquat; diethatyl; difenopenten; difenoxuron; difenzoquat;diflufenican; diflufenzopyr; dimefuron; dimepiperate; dimethachlor;dimethametryn; dimethenamid; dimethenamid-P; dimexano; dimidazon;dinitramine; dinofenate; dinoprop; dinosam; dinoseb; dinoterb;diphenamid; dipropetryn; diquat; disul; dithiopyr; diuron; DMPA; DNOC;DSMA; EBEP; eglinazine; endothal; epronaz; EPTC; erbon; esprocarb;ethalfluralin; ethametsulfuron; ethbenzamide; ethametsulfuron;ethidimuron; ethiolate; ethobenzamid; ethofumesate; ethoxyfen;ethoxysulfuron; etinofen; etnipromid; etobenzanid; EXD; fenasulam;fenoprop; fenoxaprop; fenoxaprop-P-ethyl;fenoxaprop-P-ethyl+isoxadifen-ethyl; fenoxasulfone; fenquinotrione;fenteracol; fenthiaprop; fentrazamide; fenuron; ferrous sulfate;flamprop; flamprop-M; flazasulfuron; florasulam; fluazifop;fluazifop-P-butyl; fluazolate; flucarbazone; flucetosulfuron;fluchloralin; flufenacet; flufenican; flufenpyr-ethyl; flumetsulam;flumezin; flumiclorac-pentyl; flumioxazin; flumipropyn; fluometuron;fluorodifen; fluoroglycofen; fluoromidine; fluoronitrofen; fluothiuron;flupoxam; flupropacil; flupropanate; flupyrsulfuron; fluridone;flurochloridone; fluroxypyr; fluroxypyr-meptyl; flurtamone; fluthiacet;fomesafen; foramsulfuron; fosamine; fumiclorac; furyloxyfen;glufosinate; glufosinate-ammonium; glufosinate-P-ammonium; glyphosatesalts and esters; halosafen; halosulfuron; haloxydine; haloxyfop;hexachloroacetone; hexaflurate; hexazinone; imazamethabenz; imazamox;imazapic; imazapyr; imazaquin; imazethapyr; imazosulfuron; indanofan;indaziflam; iodobonil; iodomethane; iodosulfuron;iodosulfuron-ethyl-sodium; iofensulfuron; ioxynil; ipazine;ipfencarbazone; iprymidam; isocarbamid; isocil; isomethiozin;isonoruron; isopolinate; isopropalin; isoproturon; isouron; isoxaben;isoxachlortole; isoxaflutole; isoxapyrifop; karbutilate; ketospiradox;lactofen; lenacil; linuron; MAA; MAMA; MCPA esters and amines;MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; medinoterb; mefenacet;mefluidide; mesoprazine; mesosulfuron; mesotrione; metam; metamifop;metamitron; metazachlor; metflurazon; methabenzthiazuron;methalpropalin; methazole; methiobencarb; methiozolin; methiuron;methometon; methoprotryne; methyl bromide; methyl isothiocyanate;methyldymron; metobenzuron; metobromuron; metolachlor; metosulam;metoxuron; metribuzin; metsulfuron; molinate; monalide; monisouron;monochloroacetic acid; monolinuron; monuron; morfamquat; MSMA;naproanilide; napropamide; napropamide-M; naptalam; neburon;nicosulfuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen;norflurazon; noruron; OCH; orbencarb; ortho-dichlorobenzene;orthosulfamuron; oryzalin; oxadiargyl; oxadiazon; oxapyrazon;oxasulfuron; oxaziclomefone; oxyfluorfen; paraflufen-ethyl; parafluron;paraquat; pebulate; pelargonic acid; pendimethalin; penoxsulam;pentachlorophenol; pentanochlor; pentoxazone; perfluidone; pethoxamid;phenisopham; phenmedipham; phenmedipham-ethyl; phenobenzuron;phenylmercury acetate; picloram; picolinafen; pinoxaden; piperophos;potassium arsenite; potassium azide; potassium cyanate; pretilachlor;primisulfuron; procyazine; prodiamine; profluazol; profluralin;profoxydim; proglinazine; prohexadione-calcium; prometon; prometryne;pronamide; propachlor; propanil; propaquizafop; propazine; propham;propisochlor; propoxycarbazone; propyrisulfuron; propyzamide;prosulfalin; prosulfocarb; prosulfuron; proxan; prynachlor; pydanon;pyraclonil; pyraflufen; pyrasulfotole; pyrazogyl; pyrazone;pyrazolynate; pyrazosulfuron; pyrazoxyfen; pyribenzoxim; pyributicarb;pyriclor; pyridafol; pyridate; pyriftalid; pyriminobac; pyrimisulfan;pyrithiobac-sodium; pyroxasulfone; pyroxsulam; quinclorac; quinmerac;quinoclamine; quinonamid; quizalofop; quizalofop-P-ethyl;quizalofop-P-tefuryl; rhodethanil; rimsulfuron; saflufenacil;S-metolachlor; sebuthylazine; secbumeton; sethoxydim; siduron; simazine;simeton; simetryn; SMA; sodium arsenite; sodium azide; sodium chlorate;sulcotrione; sulfallate; sulfentrazone; sulfometuron; sulfosate;sulfosulfuron; sulfuric acid; sulglycapin; swep; TCA; tebutam;tebuthiuron; tefuryltrione; tembotrione; tepraloxydim; terbacil;terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryne;tetrafluron; thenylchlor; thiameturon; thiazafluron; thiazopyr;thidiazimin; thidiazuron; thiencarbazone; thifensulfuron; thiobencarb;tiafenacil; tiocarbazil; tioclorim; tolpyralate; topramezone;tralkoxydim; tri-allate; triafamone; triasulfuron; triaziflam;tribenuron; tribenuron; tricamba; triclopyr choline salt; triclopyresters and amines; tridiphane; trietazine; trifloxysulfuron;trifludimoxazin; trifluralin; triflusulfuron; trifop; trifopsime;trihydroxytriazine; trimeturon; tripropindan; tritac; tritosulfuron;vemolate; xylachlor; and salts, esters, optically active isomers, andmixtures thereof.

In some aspects, the additional pesticide or an agriculturallyacceptable salt or ester thereof is provided in a premixed formulationwith (a), (b), or combinations thereof. In some aspects, the pyridinecarboxylate herbicide or an agriculturally acceptable N-oxide, salt, orester thereof is provided in a premixed formulation with an additionalpesticide. In some aspects, the azole carboxylate safener or anagriculturally acceptable salt or ester thereof is provided in apremixed formulation with an additional pesticide.

In some aspects, the safened compositions may include one or moreherbicidal active ingredients in addition to (a). In some aspects, thesafened compositions do not include an herbicidal active ingredient inaddition to (a). In some aspects, the safened compositions may excludeone or more herbicidal active ingredients specified above. In someaspects, the safened compositions may include one or more herbicidalactive ingredients in addition to (a), but may exclude one or moreherbicidal ingredients specified above. In some aspects, the safenedcompositions may include one or more safeners in addition to (b). Insome aspects, the safened compositions do not include a safener inaddition to (b). In some aspects, the composition may include othercomponents, such as adjuvants, but does not include a herbicidal activeingredient in addition to (a) or a safener in addition to (b).

2. Adjuvants

In some aspects, the additive includes an agriculturally acceptableadjuvant. Exemplary agriculturally acceptable adjuvants include, but arenot limited to, antifreeze agents, antifoam agents, compatibilizingagents, sequestering agents, neutralizing agents and buffers, corrosioninhibitors, colorants, odorants, penetration aids, wetting agents,spreading agents, dispersing agents, thickening agents, freeze pointdepressants, antimicrobial agents, crop oil, adhesives (for instance,for use in seed formulations), surfactants, protective colloids,emulsifiers, tackifiers, and mixtures thereof.

Exemplary agriculturally acceptable adjuvants include, but are notlimited to, crop oil concentrates (e.g., 85% mineral oil+15%emulsifiers); nonylphenol ethoxylates; benzylcocoalkyldimethyl quatemaryammonium salts; blends of petroleum hydrocarbon, alkyl esters, organicacids, and anionic surfactants; C₉-C₁₁ alkylpolyglycoside; phosphatealcohol ethoxylates; natural primary alcohol (C₁₂-C₁₆) ethoxylate;di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl cap;nonylphenol ethoxylate+urea ammonium nitrates; emulsified methylatedseed oils; tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO); tallowamine ethoxylates (e.g., 15 EO); and PEG(400) dioleate-99.

Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants,emulsifiers) include, but are not limited to: the alkali metal salts,alkaline earth metal salts and ammonium salts of fatty acids or ofaromatic sulfonic acids (e.g., lignosulfonic acids, phenolsulfonicacids, naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid);alkyl- and alkylarylsulfonates; alkyl sulfates, lauryl ether sulfatesand fatty alcohol sulfates; salts of sulfated hexa-, hepta- andoctadecanols; salts of fatty alcohol glycol ethers; condensates ofsulfonated naphthalene and its derivatives with formaldehyde;condensates of naphthalene or of the naphthalene sulfonic acids withphenol and formaldehyde; polyoxyethylene octylphenol ether; ethoxylatedisooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenylpolyglycol ether; alkyl aryl polyether alcohols; isotridecyl alcohol;fatty alcohol/ethylene oxide condensates; ethoxylated castor oil;polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers; laurylalcohol polyglycol ether acetate; sorbitol esters; lignosulfite wasteliquors and proteins; denatured proteins, polysaccharides (e.g.,methylcellulose); hydrophobically modified starches; and polyvinylalcohol, polycarboxylates, polyalkoxylates, polyvinyl amine,polyethyleneimine, polyvinylpyrrolidone, and copolymers thereof.

Exemplary thickeners include, but are not limited to, polysaccharides(e.g., xanthan gum), organic and inorganic sheet minerals, and mixturesthereof.

Exemplary antifoam agents include, but are not limited to, siliconeemulsions, long-chain alcohols, fatty acids, fatty acid salts,organofluorine compounds, and mixtures thereof.

Exemplary antimicrobial agents include, but are not limited to:bactericides based on dichlorophen and benzyl alcohol hemiformal;isothiazolinone derivatives, such as alkylisothiazolinones andbenzisothiazolinones; and mixtures thereof.

Exemplary antifreeze agents, include, but are not limited to ethyleneglycol, propylene glycol, urea, glycerol, and mixtures thereof.

Exemplary colorants include, but are not limited to, the dyes knownunder the names Rhodamine B, pigment blue 15:4, pigment blue 15:3,pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1,pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1,pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange34, pigment orange 5, pigment green 36, pigment green 7, pigment white6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acidred 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basicred 108, and mixtures thereof.

Exemplary adhesives include, but are not limited to,polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, andmixtures thereof.

3. Carriers

In some aspects, the additive includes a carrier. In some aspects, theadditive includes a liquid or solid carrier. In some aspects, theadditive includes an organic or inorganic carrier. Exemplary liquidcarriers include, but are not limited to: water; petroleum fractions orhydrocarbons such as mineral oil, aromatic solvents, paraffinic oils,and the like; vegetable oils such as soybean oil, rapeseed oil, oliveoil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseedoil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tungoil and the like; esters of the above vegetable oils; esters ofmonoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6hydroxy containing), such as 2-ethyl hexyl stearate, n-butyl oleate,isopropyl myristate, propylene glycol dioleate, di-octyl succinate,di-butyl adipate, di-octyl phthalate and the like; esters of mono, diand polycarboxylic acids and the like; toluene; xylene; petroleumnaphtha; crop oil; acetone; methyl ethyl ketone; cyclohexanone;trichloroethylene; perchloroethylene; ethyl acetate; amyl acetate; butylacetate; propylene glycol monomethyl ether and diethylene glycolmonomethyl ether; methyl alcohol; ethyl alcohol; isopropyl alcohol; amylalcohol; ethylene glycol; propylene glycol; glycerin;N-methyl-2-pyrrolidinone; N;N-dimethyl alkylamides; dimethyl sulfoxide;and liquid fertilizers, as well as mixtures thereof. Exemplary solidcarriers include, but are not limited to: silicas, silica gels,silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay,dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, pyrophyllite clay,attapulgus clay, kieselguhr, calcium carbonate, bentonite clay, Fuller'searth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour,walnut shell flour, lignin, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal andnutshell meal, cellulose powders, and mixtures thereof.

B. Physical States

In some aspects, the formulation of (a) the pyridine carboxylateherbicide or an agriculturally acceptable N-oxide, salt, or esterthereof and (b) the azole carboxylate safener or an agriculturallyacceptable salt or ester thereof may be present in suspended,emulsified, dissolved, or solid form. Exemplary formulations include,but are not limited to, aqueous solutions, aqueous suspensions, aqueousdispersions, aqueous emulsions, aqueous microemulsions, aqueoussuspo-emulsions, oil solutions, oil suspensions, oil dispersions, oilemulsions, oil microemulsions, oil suspo-emulsions, self-emulsifyingformulations, pastes, powders, dusts, granules, and materials forspreading.

In some aspects, (a) the pyridine carboxylate herbicide or anagriculturally acceptable N-oxide, salt, or ester thereof or (b) theazole carboxylate safener or an agriculturally acceptable salt or esterthereof are aqueous solutions that can be diluted before use. In variousaspects, (a) or (b) are provided as a high-strength formulation such asa concentrate. In some aspects, the concentrate is stable and retainspotency during storage and shipping. In various aspects, the concentrateis a clear, homogeneous liquid that is stable at temperatures of 54° C.or greater. In some aspects, the concentrate does not exhibit anyprecipitation of solids at temperatures of −10° C. or higher. In someaspects, the concentrate does not exhibit separation, precipitation, orcrystallization of any components at low temperatures. For example, theconcentrate remains a clear solution at temperatures below 0° C. (e.g.,below −5° C., below −10° C., below −15° C.). In some aspects, theconcentrate exhibits a viscosity of less than 50 centipoise (50megapascals), even at temperatures as low as 5° C. In some aspects, theconcentrate does not exhibit separation, precipitation, orcrystallization of any components during storage for a period of 2 weeksor greater (e.g., 4 weeks, 6 weeks, 8 weeks, 3 months, 6 months, 9months, or 12 months or greater).

In some aspects, emulsions, pastes, or oil dispersions can be preparedby homogenizing (a) and (b) in water with a wetting agent, tackifier,dispersant, or emulsifier. In some aspects, concentrates suitable fordilution with water can be prepared, comprising (a), (b), a wettingagent, a tackifier, and a dispersant or emulsifier.

In some aspects, powders, materials for spreading, or dusts can beprepared by mixing or concomitant grinding of (a) and (b) and optionallyother additives with a solid carrier.

In some aspects, granules (e.g., coated granules, impregnated granulesand homogeneous granules) can be prepared by binding the (a) and (b) tosolid carriers.

In some aspects, the formulations comprise from 1% to 99% of (a) and 1%to 99% of (b) (e.g., 95% of (a) and 5% of (b); 70% of (a) and 30% of(b); or 30% of (a) and 70% of (b)) by total weight of (a) and (b). Informulations designed to be employed as concentrates, the total amountof (a) and (b) can be present in a concentration of from about 0.1 toabout 98 weight percent (wt. %), based on the total weight of theformulation. For example, the total amount of (a) and (b) can be presentin a concentration as little as about 1 wt. %, about 2.5 wt. %, about 5wt. %, about 7.5 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %,about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45wt. %, as high as about 50 wt. %, about 55 wt. %, about 60 wt. %, about65 wt. %, about 70 wt. %, about 75 wt. %, about 80 wt. %, about 85 wt.%, about 90 wt. %, about 95 wt. %, about 97 wt. %, or within any rangedefined between any two of the forgoing values, such as between about 1wt. % to about 97 wt. %, between about 10 wt. % to about 90 wt. %,between about 20 wt. % to about 45 wt. %, and about 25 wt. % to about 50wt. % based on the total weight of the formulation. Concentrates can bediluted with an inert carrier, such as water, prior to application. Thediluted formulations applied to undesirable vegetation or the locus ofundesirable vegetation can contain from 0.0006 to 8.0 wt. % of the totalamount of (a) and (b) (e.g., from 0.001 to 5.0 wt. %), based on thetotal weight of the diluted formulation.

C. Packaging

In some aspects, the formulation can be in the form of a single packageformulation including both: (a) the pyridine carboxylate herbicide or anagriculturally acceptable N-oxide, salt, or ester thereof; and (b) theazole carboxylate safener or an agriculturally acceptable salt or esterthereof. In some aspects, the formulation can be in the form of a singlepackage formulation including both (a) and (b) and further including atleast one additive. In some aspects, the formulation can be in the formof a multi-package formulation, such as a two-package formulation,wherein one package contains (a) and optionally at least one additivewhile the other package contains (b) and optionally at least oneadditive. In some aspects of the two-package formulation, theformulation including (a) and optionally at least one additive and theformulation including (b) and optionally at least one additive are mixedbefore application and then applied simultaneously. In some aspects, themixing is performed as a tank mix (e.g., the formulations are mixedimmediately before or upon dilution with water). In some aspects, theformulation including (a) and the formulation including (b) are notmixed but are applied sequentially (in succession), for example,immediately or within 1 hour, within 2 hours, within 4 hours, within 8hours, within 16 hours, within 24 hours, within 2 days, or within 3days, of each other.

VI. Methods of Use

The compositions disclosed herein can be applied in any known techniquefor applying herbicides. Exemplary application techniques include, butare not limited to, spraying, atomizing, dusting, spreading, or directapplication into water. The method of application can vary depending onthe intended purpose. In some aspects, the method of application can bechosen to ensure the finest possible distribution of the compositionsdisclosed herein.

In some aspects, a method of controlling undesirable vegetation whichcomprises contacting the vegetation or the locus thereof with orapplying to the soil or water to prevent the emergence or growth ofvegetation any of the compositions is disclosed herein.

The compositions disclosed herein can be applied pre-emergence (beforethe emergence of undesirable vegetation) or post-emergence (e.g., duringand/or after emergence of the undesirable vegetation). In some aspects,the composition is applied post-emergence to the undesirable vegetation.In some aspects, the pyridine carboxylate herbicide and azolecarboxylate safener are applied simultaneously. In some aspects, thepyridine carboxylate herbicide and azole carboxylate safener are appliedsequentially, for example, immediately or with minimal delay, withinabout 10 minutes, within about 20 minutes, within about 30 minutes,within about 40 minutes, within about 1 hour, within about 2 hours,within about 4 hours, within about 8 hours, within about 16 hours,within about 24 hours, within about 2 days, or within about 3 days, ofeach other.

In some aspects, the pyridine carboxylate herbicide can be appliedpre-emergently or post-emergently to the undesirable vegetation and theazole carboxylate safener can be applied as a seed treatment to the cropseeds. When applied as a seed treatment, the azole carboxylate safeneris applied at rate from 0.01 to 10 g ai of safener per kg (g ai/kg) ofcrop seed, preferably 0.05 to 1 g ai/kg of crop seed, in particular 0.1to 0.5 g ai/kg of crop seed. If solutions of safeners are used to treatthe seeds, the concentration of the safener in the solution is, forexample, from 1 to 10000 ppm, preferably 100 to 1000 ppm, based onweight.

When the compositions are used in crops, the compositions can be appliedafter seeding and before or after the emergence of the crop plants. Insome aspects, the compositions disclosed herein show good crop toleranceeven when the crop has already emerged and can be applied during orafter the emergence of the crop plants. In some aspects, when thecompositions are used in crops, the compositions can be applied beforeseeding of the crop plants.

In some aspects, the compositions disclosed herein are applied tovegetation or an area adjacent the vegetation or applying to soil orwater to prevent the emergence or growth of vegetation by spraying(e.g., foliar spraying). In some aspects, the spraying techniques use,for example, water as carrier and spray volume rates of from 2 litersper hectare (L/ha) to 2000 L/ha (e.g., from 10-1000 L/ha or from 50-500L/ha). In some aspects, the compositions disclosed herein are applied bythe low-volume or the ultra-low-volume method, wherein the applicationis in the form of micro granules. In some aspects, wherein thecompositions disclosed herein are less well tolerated by certain cropplants, the compositions can be applied with the aid of the sprayapparatus in such a way that they come into little contact, if any, withthe leaves of the sensitive crop plants while reaching the leaves ofundesirable vegetation that grows underneath or on the bare soil (e.g.,post-directed or lay-by). In some aspects, the compositions disclosedherein can be applied as dry formulations (e.g., granules, powders, ordusts).

In some aspects, wherein the undesirable vegetation is treatedpost-emergence, the compositions disclosed herein are applied by foliarapplication. In some aspects, herbicidal activity is exhibited by thecompounds of the mixture when they are applied directly to the plant orto the locus of the plant at any stage of growth or before planting oremergence. The effect observed can depend upon the type of undesirablevegetation to be controlled, the stage of growth of the undesirablevegetation, the application parameters of dilution and spray drop size,the particle size of solid components, the environmental conditions atthe time of use, the specific compound employed, the specific adjuvantsand carriers employed, the soil type, and the like, as well as theamount of chemical applied. In some aspects, these and other factors canbe adjusted to promote non-selective or selective herbicidal action.

The compositions and methods disclosed herein can be used to controlundesirable vegetation in a variety of applications. The compositionsand methods disclosed herein can be used for controlling undesirablevegetation in areas including, but not limited to, farmland, turfgrass,pastures, grasslands, rangelands, fallow land, rights-of-way, aquaticsettings, tree and vine, wildlife management areas, or rangeland. Insome aspects, the undesirable vegetation is controlled in a row crop.Exemplary crops include, but are not limited to, wheat, barley,triticale, rye, teff, oats, maize, cotton, soy, sorghum, rice, millet,sugarcane and range land (e.g., pasture grasses). In some aspects, thecompositions and methods disclosed herein can be used for controllingundesirable vegetation in maize, wheat, barley, rice, sorghum, millet,or oats, or combinations thereof. In some aspects, the compositions andmethods disclosed herein can be used for controlling undesirablevegetation in broadleaf crops. In some aspects, the compositions andmethods disclosed herein can be used for controlling undesirablevegetation in canola, flax, sunflower, soy, or cotton. In some aspects,the compositions and methods disclosed herein can be used in industrialvegetation management (IVM) or for utility, pipeline, roadside, andrailroad rights-of-way applications. In some aspects, the compositionsand methods disclosed herein can also be used in forestry (e.g., forsite preparation or for combating undesirable vegetation in plantationforests). In some aspects, the compositions and methods disclosed hereincan be used to control undesirable vegetation in conservation reserveprogram lands (CRP), trees, vines, grasslands, and grasses grown forseeds. In some aspects, the compositions and methods disclosed hereincan be used on lawns (e.g., residential, industrial, and institutional),golf courses, parks, cemeteries, athletic fields, and sod farms.

The compositions and methods disclosed herein can also be used in cropplants that are resistant to, for instance, herbicides, pathogens,and/or insects. In some aspects, the compositions and methods disclosedherein can be used in crop plants that are resistant to one or moreherbicides because of genetic engineering or breeding. In some aspects,the compositions and methods disclosed herein can be used in crop plantsthat are resistant to one or more pathogens such as plant pathogenicfungi owing to genetic engineering or breeding. In some aspects, thecompositions and methods disclosed herein can be used in crop plantsthat are resistant to attack by insects owing to genetic engineering orbreeding. Exemplary resistant crops include, but are not limited to,crops that are resistant to photosystem II inhibitors, or crop plantsthat, owing to introduction of the gene for Bacillus thuringiensis (orBt) toxin by genetic modification, are resistant to attack by certaininsects. In some aspects, the compositions and methods described hereincan be used in conjunction with glyphosate, glufosinate, dicamba,phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoAcarboxylase (ACCase) inhibitors, imidazolinones, acetolactate synthase(ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD)inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, andbromoxynil to control vegetation in crops tolerant to glyphosate,glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins,aryloxyphenoxypropionates, ACCase inhibitors, imidazolinones, ALSinhibitors, HPPD inhibitors, PPO inhibitors, triazines, bromoxynil, orcombinations thereof. In some aspects, the undesirable vegetation iscontrolled in glyphosate, glufosinate, dicamba, phenoxy auxins,pyridyloxy auxins, aryloxyphenoxypropionates, ACCase inhibitors, ALSinhibitors, HPPD inhibitors, PPO inhibitors, triazines, and bromoxyniltolerant crops possessing single, multiple or stacked traits conferringtolerance to single or multiple chemistries and/or multiple modes ofaction. In some aspects, the undesirable vegetation can be controlled ina crop that is ACCase-tolerant, ALS-tolerant, or a combination thereof.The combination of (a) and (b) can be used in combination with one ormore herbicides that are selective for the crop being treated and whichcomplement the spectrum of weeds controlled by these compounds at theapplication rate employed. In some aspects, the compositions describedherein and other complementary herbicides are applied at the same time,either as a combination formulation or as a tank mix, or as sequentialapplications. The compositions and methods may be used in controllingundesirable vegetation in crops possessing agronomic stress tolerance(including but not limited to drought, cold, heat, salt, water,nutrient, fertility, pH), pest tolerance (including but not limited toinsects, fungi and pathogens), and crop improvement traits (includingbut not limited to yield; protein, carbohydrate, or oil content;protein, carbohydrate, or oil composition; plant stature and plantarchitecture).

In some aspects, the compositions disclosed herein can be used forcontrolling undesirable vegetation including grasses, broadleaf weeds,sedge weeds, and combinations thereof. In some aspects, the compositionsdisclosed herein can be used for controlling undesirable vegetationincluding, but not limited to, Polygonum species, Amaranthus species,Chenopodium species, Sida species, Ambrosia species, Cyperus species,Setaria species, Sorghum species, Acanthospermum species, Anthemisspecies, Atriplex species, Brassica species, Cirsium species,Convolvulus species, Conyza species, Cassia species, Commelina species,Datura species, Euphorbia species, Geranium species, Galinsoga species,Ipomea species, Lamium species, Lolium species, Malva species,Matricaria species, Prosopis species, Rumex species, Sisymbrium species,Solanum species, Trifolium species, Xanthium species, Veronica species,and Viola species. In some aspects, the undesired vegetation includescommon chickweed (Stellaria media), velvetleaf (Abutilon theophrasti),hemp sesbania (Sesbania exaltata Cory), Anoda cristata, Bidens pilosa,Brassica kaber, shepherd's purse (Capsella bursa-pastoris), cornflower(Centaurea cyanus or Cyanus segetum), hempnettle (Galeopsis tetrahit),cleavers (Galium aparine), common sunflower (Helianthus annuus),Desmodium tortuosum, Italian ryegrass (Lolium multiflorum), kochia(Kochia scoparia), Medicago arabica, Mercurialis annua, Myosotisarvensis, common poppy (Papaver rhoeas), Raphanus raphanistrum,broad-leaf dock (Rumex obtusifolius), Russian thistle (Salsola kali),wild mustard (Sinapis arvensis), Sonchus arvensis, Thlaspi arvense,Tagetes minuta, Richardia brasiliensis, Plantago major, Plantagolanceolata, bird's-eye speedwell (Veronica persica), pigweed (Amaranthusretroflexus), winter rape (Brassica napus), lambsquarters (Chenopodiumalbum), Canada thistle (Cirsium arvense), nutsedge (Cyperus esculentus),poinsettia (Euphorbiaheterophylla), prickly lettuce (Lactuca serriola),purple deadnettle (Lamium purpureum), wild chamomile (Matricariachamomilla), false chamomile (Matricaria inodora), field chamomile(Anthemis arvensis), common buckwheat (Fagopyrum esculentum), wildbuckwheat (Polygonum convulvus), giant foxtail (Setaria faberi), greenfoxtail (Setaria viridis), common sorghum (Sorghum vulgare), wild pansy(Viola tricolor), or combinations thereof.

The compositions described herein can be used to control herbicideresistant or tolerant weeds. The methods employing the compositionsdescribed herein may also be employed to control herbicide resistant ortolerant weeds. Exemplary resistant or tolerant weeds include, but arenot limited to, biotypes resistant or tolerant to acetolactate synthase(ALS) or acetohydroxy acid synthase (AHAS) inhibitors (e.g.,imidazolinones, sulfonylureas, pyrimidinylthiobenzoates,triazolopyrimidines, sulfonylaminocarbonyltriazolinones), photosystem IIinhibitors (e.g., phenylcarbamates, pyridazinones, triazines,triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles,phenylpyridazines), acetyl CoA carboxylase (ACCase) inhibitors (e.g.,aryloxyphenoxypropionates, cyclohexanediones, phenylpyrazolines),synthetic auxins (e.g., benzoic acids, phenoxycarboxylic acids, pyridinecarboxylates, quinoline carboxylic acids), auxin transport inhibitors(e.g., phthalamates, semicarbazones), photosystem I inhibitors (e.g.,bipyridyliums), 5-enolpyruvylshikimate-3-phosphate (EPSP) synthaseinhibitors (e.g., glyphosate), glutamine synthetase inhibitors (e.g.,glufosinate, bialaphos), microtubule assembly inhibitors (e.g.,benzamides, benzoic acids, dinitroanilines, phosphoramidates,pyridines), mitosis inhibitors (e.g., carbamates), very long chain fattyacid (VLCFA) inhibitors (e.g., acetamides, chloroacetamides,oxyacetamides, tetrazolinones), fatty acid and lipid synthesisinhibitors (e.g., phosphorodithioates, thiocarbamates, benzofuranes,chlorocarbonic acids), protoporphyrinogen oxidase (PPO) inhibitors(e.g., diphenylethers, N-phenylphthalimides, oxadiazoles,oxazolidinediones, phenylpyrazoles, pyrimidindiones, thiadiazoles,triazolinones), carotenoid biosynthesis inhibitors (e.g., clomazone,amitrole, aclonifen), phytoene desaturase (PDS) inhibitors (e.g.,amides, anilidex, furanones, phenoxybutan-amides, pyridiazinones,pyridines), 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD) inhibitors(e.g., callistemones, isoxazoles, pyrazoles, triketones), cellulosebiosynthesis inhibitors (e.g., nitriles, benzamides, quinclorac,triazolocarboxamides), herbicides with multiple modes of action such asquinclorac, and unclassified herbicides such as arylaminopropionicacids, difenzoquat, endothall, and organoarsenicals. Exemplary resistantor tolerant weeds include, but are not limited to, biotypes withresistance or tolerance to multiple herbicides, biotypes with resistanceor tolerance to multiple chemical classes, biotypes with resistance ortolerance to multiple herbicide modes of action, and biotypes withmultiple resistance or tolerance mechanisms (e.g., target siteresistance or metabolic resistance).

By way of non-limiting illustration, examples of some aspects of thepresent disclosure are given below. Parts and percentages are on a perweight basis unless otherwise indicated.

EXAMPLES Greenhouse Trial Methodology—Evaluation of PostemergenceHerbicidal Safening in Crops

Seeds of the desired test plant species were planted in a 90:10% v/v(volume/volume) mixture of PRO-MIX® BX (Premier Tech Horticulture,Quakertown, Pa., USA) and PROFILE® GREENS GRADE™ (Profile Products LLC,Buffalo Grove, Ill., USA) planting mixture, which typically has a pH of5.2 to 6.2 and an organic matter content of at least 50 percent, inplastic pots with a surface area of 103.2 square centimeters (cm²). Whenrequired to ensure good germination and healthy plants, a fungicidetreatment and/or other chemical or physical treatment was applied. Theplants were grown for 7-36 days (d) in a greenhouse with an approximate14-hour (h) photo-period which was maintained at about 23° C. during theday and 22° C. during the night. Nutrients and water were added on aregular basis and supplemental lighting was provided with overhead metalhalide 1000-Watt lamps as necessary. The plants were employed fortesting when they reached the second or third true leaf stage.

Emulsifiable concentrates of each of each pyridine carboxylate herbicide(Compound A or Compound B) were prepared at 100 grams acid equivalentper liter (g ae/L). An aliquot of each emulsifiable concentrate wasplaced in a 25 mL glass vial and diluted with an aqueous mixture of1.25% (v/v) ACTIROB® B esterified rapeseed oil (Bayer Crop Science,Research Triangle Park, NC, USA) or MSO® Concentrate with LECI-TECH®methylated soybean oil (Loveland Products, Loveland, Colo., USA) toobtain concentrated stock solutions at the highest application rate foreach herbicide, based upon a 12 milliliter (mL) application volume at arate of 187 liters per hectare (L/ha). The concentrated stock solutionswere further diluted with an aqueous mixture of 1.25% v/v ACTIROB® B orMSO® Concentrate with LECI-TECH® to obtain stock solutions at reducedapplication rates for each herbicide. Spray solutions of the herbicidecombinations (Compound A or Compound B plus safener) were prepared byadding weighed amounts or aliquots of the azole carboxylate safener tothe stock solutions of Compound A or Compound B to form 12-mL spraysolutions in two-way combinations.

The spray solutions were applied to the plant material with an overheadMandel track sprayer equipped with 8002E nozzles calibrated to deliver187 L/ha over an application area of 0.503 square meters (m²) at a sprayheight of 18 inches (43 centimeters (cm)) above the average plantcanopy. Control plants were sprayed in the same manner with the solventblank. All herbicide (component a) application rates are given as “gae/ha” and all safener (component b) application rates are given as “gai/ha.”

The treated plants and control plants were placed in a greenhouse asdescribed above and watered by sub-irrigation to prevent wash-off of thetest compounds. After 20-22 d, the condition of the test plants ascompared with that of the control plants was determined visually andscored on a scale of 0 to 100 percent where 0 corresponds to no injuryand 100 corresponds to complete kill.

The details of the safened compositions and the crops tested arespecified in the following Examples.

Example 1

A safened composition comprising fenchlorazole-ethyl and Compound A wastested on spring wheat (TRZAS) and spring barley (HORVS), and thephytotoxicity of the safened composition on each crop was measured. Inaddition, the efficacy of the safened compositions on undesirablevegetation, including winter rape (BRSNW, Brassica napus), wildchamomile (MATCH, Matricaria chamomilla), and Russian thistle (SASKR,Salsola kali), was measured.

The results are summarized in Table 1 below.

TABLE 1 Safening of Effects (% visual injury) of Fenchlorazole-ethyl andCompound A on grain crops and weeds. Application Compound A 20 0 0 0 2020 20 rate (g/ha) Fenchlorazole- 0 10 20 40 10 20 40 ethyl Herbicide:2:1 1:1 1:2 Safener Ratio TRZAS Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ−25 −25 −25 HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 BRSNW Ob 950 0 0 80 95 Ex — — — — 95 95 Δ −15 0 MATCH Ob 50 0 0 0 50 50 Ex — — — —50 50 Δ 0 0 SASKR Ob 60 0 0 0 65 65 Ex — — — — 60 60 Δ 5 5 g/ha = gramsper hectare TRZAS = Triticum aestivum (spring wheat) HORVS = Hordeumvulgare (spring barley) BRSNW = Brassica napus (winter rape) MATCH =Matricaria chamomilla (wild chamomile) SASKR = Salsola kali (Russianthistle)

Example 2

A safened composition comprising mefenpyr-diethyl and Compound A wastested on spring barley (HORVS), spring wheat (TRZAS), and winter wheat(TRZAW), and the phytotoxicity of the safened composition on each cropwas measured.

The results are summarized in Table 2 below.

TABLE 2 Safening of Effects (% visual injury) of Mefenpyr-diethyl andCompound A on grain crops. Application Compound A 40 0 0 0 0 40 40 40 40rate (g/ha) Mefenpyr-diethyl 0 20 40 80 120 20 40 80 120 Herbicide: 2:11:1 1:2 1:3 Safener Ratio HORVS Ob 17 0 0 0 0 0 0 0 0 Ex — — — — — 17 1717 17 Δ −17 −17 −17 −17 TRZAS Ob 23 0 0 0 0 0 0 0 0 Ex — — — — — 23 2323 23 Δ −23 −23 −23 −23 TRZAW Ob 25 0 0 0 0 0 0 0 0 Ex — — — — — 25 2525 25 Δ −25 −25 −25 −25 g/ha = grams per hectare HORVS = Hordeum vulgare(spring barley) TRZAS = Triticum aestivum (spring wheat) TRZAW =Triticum aestivum (winter wheat)

Example 3

A safened composition comprising mefenpyr-diethyl and Compound A wastested on spring wheat (TRZAS), and the phytotoxicity of the safenedcomposition on this crop was measured. In addition, the efficacy of thesafened compositions on undesirable vegetation, including pigweed(AMARE, Amaranthus retroflexus), nutsedge (CYPES, Cyperus esculentus),and common sunflower (HELAN, Helianthus annuus), was measured.

The results are summarized in Table 3 below.

TABLE 3 Safening of Effects (% visual injury) of Mefenpyr-diethyl andCompound A on grain crops and weeds. Application Compound A 40 0 0 0 040 40 40 40 rate (g/ha) Mefenpyr-diethyl 0 20 40 80 120 20 40 80 120Herbicide: 2:1 1:1 1:2 1:3 Safener Ratio TRZAS Ob 30 0 0 0 0 0 0 0 5 Ex— — — — — 30 30 30 30 Δ −30 −30 −30 −25 AMARE Ob 100 0 0 0 0 100 100 100100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 CYPES Ob 73 0 0 0 0 85 85 8785 Ex — — — — — 73 73 73 73 Δ 13 13 14 13 HELAN Ob 100 0 0 0 0 100 100100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 g/ha = grams per hectareTRZAS = Triticum aestivum (spring wheat) AMARE = Amaranthus retroflexus(pigweed) CYPES = Cyperus esculentus (nutsedge) HELAN = Helianthusannuus (common sunflower)

Example 4

A safened composition comprising mefenpyr-diethyl and Compound A wastested on spring wheat (TRZAS) and spring barley (HORVS), and thephytotoxicity of the safened composition on each crop was measured. Inaddition, the efficacy of the safened compositions on undesirablevegetation, including wild chamomile (MATCH, Matricaria chamomilla), andRussian thistle (SASKR, Salsola kali), was measured.

The results are summarized in Table 4 below.

TABLE 4 Safening of Effects (% visual injury) of Mefenpyr-diethyl andCompound A on grain crops and weeds. Application Compound A 20 0 0 0 2020 20 rate (g/ha) Mefenpyr-diethyl 0 10 20 40 10 20 40 Herbicide: 2:11:1 1:2 Safener Ratio TRZAS Ob 25 0 0 0 0 3 0 Ex — — — — 25 25 25 Δ −25−23 −25 HORVS Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 MATCH Ob 50 0 00 60 60 Ex — — — — 50 50 Δ 10 10 SASKR Ob 60 0 0 0 65 65 Ex — — — — 6060 Δ 5 5 g/ha = grams per hectare TRZAS = Triticum aestivum (springwheat) HORVS = Hordeum vulgare (spring barley) MATCH = Matricariachamomilla (wild chamomile) SASKR = Salsola kali (Russian thistle)

Example 5

A safened composition comprising mefenpyr-diethyl and Compound A wastested on maize (ZEAMX), and the phytotoxicity of the safenedcomposition on this crop was measured. In addition, the efficacy of thesafened compositions on undesirable vegetation, including pigweed(AMARE, Amaranthus retroflexus), nutsedge (CYPES, Cyperus esculentus),and common sunflower (HELAN, Helianthus annuus), was measured.

The results are summarized in Table 5.

TABLE 5 Safening of Effects (% visual injury) of Mefenpyr-diethyl andCompound A on maize and weeds. Application Compound A 40 0 0 0 0 40 4040 40 rate (g/ha) Mefenpyr-diethyl 0 20 40 80 120 20 40 80 120Herbicide: 2:1 1:1 1:2 1:3 Safener Ratio ZEAMX Ob 55 0 0 0 0 35 28 25 20Ex — — — — — 55 55 55 55 Δ −20 −28 −30 −35 AMARE Ob 100 0 0 0 0 100 100100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 CYPES Ob 73 0 0 0 0 85 8587 85 Ex — — — — — 73 73 73 73 Δ 13 13 14 13 HELAN Ob 100 0 0 0 0 100100 100 100 Ex — — — — — 100 100 100 100 Δ 0 0 0 0 g/ha = grams perhectare ZEAMX = Zea mays (maize) AMARE = Amaranthus retroflexus(pigweed) CYPES = Cyperus esculentus (nutsedge) HELAN = Helianthusannuus (common sunflower)

Example 6

A safened composition comprising fenchlorazole and Compound A was testedon winter wheat (TRZAW), rice (ORYSA), and maize (ZEAMX), and thephytotoxicity of the safened composition on the crops was measured. Inaddition, the efficacy of the safened compositions on undesirablevegetation, including velvetleaf (ABUTH, Abutilon theophrasti),blackgrass (ALOMY, Alopecurus myosuroides), pigweed (AMARE, Amaranthusretroflexus), wild oat (AVEFA, Avena fatua), winter rape (BRSNW,Brassica napus), common lambsquarters (CHEAL, Chenopodium album L.),Canada thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperusesculentus), large crabgrass (DIGSA, Digitaria sanguinalis),bamyardgrass (ECHCG, Echinochloa crus-galli), Canada horseweed (ERICA,Erigeron canadensis), soybean (GLXMA, Glycine max), common sunflower(HELAN, Helianthus annuus), ivyleaf morningglory (IPOHE, Ipomoeahederacea), kochia (KCHSC, Kochia scoparia), herbicide-resistant kochia(KCHSC-R, Kochia scoparia), Chinese sprangletop (LEFCH, Leptochloachinensis), Italian ryegrass (LOLMU, Lolium multiflorum), wild buckwheat(POLCO, Polygonum convolvulus), giant foxtail (SETFA, Setaria faberi),Johnson grass (SORHA, Sorghum halepense), and wild pansy (VIOTR, Violatricolor) was measured.

The results are summarized in Table 6 below.

TABLE 6 Safening of Effects (% visual injury) of Fenchlorazole andCompound A on crops and weeds. Application Compound A 20 0 0 0 20 20 20rate (g/ha) Fenchlorazole 0 20 40 80 20 40 80 Herbicide: 1:1 1:2 1:4Safener Ratio TRZAW Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25 −25ORYSA Ob 10 0 0 0 10 10 15 Ex — — — — 10 10 10 Δ 0 0 5 ZEAMX Ob 13 0 0 05 10 10 Ex — — — — 13 13 13 Δ −8 −3 −3 ABUTH Ob 95 0 0 0 95 97 97 Ex — —— — 95 95 95 Δ 0 2 2 ALOMY Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0AMARE Ob 93 0 0 0 100 100 100 Ex — — — — 93 93 93 Δ 7 7 7 AVEFA Ob 0 0 00 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 BRSNW Ob 85 0 0 0 95 90 100 Ex — — — —85 85 85 Δ 10 −5 15 CHEAL Ob 88 0 0 0 100 100 100 Ex — — — — 88 88 88 Δ12 12 12 CIRAR Ob 95 0 0 0 70 70 65 Ex — — — — 95 95 95 Δ −25 −25 −30CYPES Ob 30 0 0 0 30 35 35 Ex — — — — 30 30 30 Δ 0 5 5 DIGSA Ob 30 0 0 040 10 10 Ex — — — — 30 30 30 Δ 10 −20 −20 ECHCG Ob 85 0 0 0 80 90 90 Ex— — — — 85 85 85 Δ −5 5 5 ERICA Ob 95 0 0 0 97 95 97 Ex — — — — 95 95 95Δ 2 0 2 GLXMA Ob 100 0 0 0 100 100 100 Ex — — — — 100 100 100 Δ 0 0 0HELAN Ob 95 0 0 0 100 100 100 Ex — — — — 95 95 95 Δ 5 5 5 IPOHE Ob 0 0 00 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 KCHSC Ob 97 0 0 0 97 97 97 Ex — — — —97 97 97 Δ 0 0 0 KCHSC-R Ob 90 0 0 0 85 90 90 Ex — — — — 90 90 90 Δ −5 00 LEFCH Ob 60 0 0 0 30 30 30 Ex — — — — 60 60 60 Δ −30 −30 −30 LOLMU Ob5 0 0 0 5 5 5 Ex — — — — 5 5 5 Δ 0 0 0 POLCO Ob 100 0 0 0 100 100 100 Ex— — — — 100 100 100 Δ 0 0 0 SETFA Ob 65 0 0 0 75 70 60 Ex — — — — 65 6565 Δ 10 5 −5 SORHA Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 VIOTR Ob 300 0 0 20 20 20 Ex — — — — 30 30 30 Δ −10 −10 −10 g/ha = grams perhectare TRZAW = Triticum aestivum (winter wheat) ORYSA = Oryza sativa(common rice) ZEAMX = Zea mays (maize) ABUTH = Abutilon theophrasti(velvetleaf) ALOMY = Alopecurus myosuroides (blackgrass) AMARE =Amaranthus retroflexus (pigweed) AVEFA = Avena fatua (wild oat) BRSNW =Brassica napus (winter rape) CHEAL = Chenopodium album L. (commonlambsquarters) CIRAR = Cirsium arvense (Canada thistle) CYPES = Cyperusesculentus (nutsedge) DIGSA = Digitaria sanguinalis (large crabgrass)ECHCG = Echinochloa crus-galli (barnyardgrass) ERICA = Erigeroncanadensis (Canada horseweed) GLXMA = Glycine max (soybean) HELAN =Helianthus annuus (common sunflower) IPOHE = Ipomoea hederacea (ivyleafmorningglory) KCHSC = Kochia scoparia (kochia) KCHSC-R = Kochia scoparia(herbicide-resistant kochia) LEFCH = Leptochloa chinensis (Chinesesprangletop) LOLMU = Lolium multiflorum (Italian ryegrass) POLCO =Polygonum convolvulus (wild buckwheat) SETFA = Setaria faberi (giantfoxtail) SORHA = Sorghum halepense (Johnson grass) VIOTR = Violatricolor (wild pansy)

Example 7

A safened composition comprising mefenpyr-diethyl and Compound A wastested on winter wheat (TRZAW), rice (ORYSA), and maize (ZEAMX), and thephytotoxicity of the safened composition on the crops was measured. Inaddition, the efficacy of the safened compositions on undesirablevegetation, including velvetleaf (ABUTH, Abutilon theophrasti),blackgrass (ALOMY, Alopecurus myosuroides), pigweed (AMARE, Amaranthusretroflexus), wild oat (AVEFA, Avena fatua), winter rape (BRSNW,Brassica napus), common lambsquarters (CHEAL, Chenopodium album L.),Canada thistle (CIRAR, Cirsium arvense), nutsedge (CYPES, Cyperusesculentus), large crabgrass (DIGSA, Digitaria sanguinalis),bamyardgrass (ECHCG, Echinochloa crus-galli), Canada horseweed (ERICA,Erigeron canadensis), soybean (GLXMA, Glycine max), common sunflower(HELAN, Helianthus annuus), ivyleaf morningglory (IPOHE, Ipomoeahederacea), kochia (KCHSC, Kochia scoparia), herbicide-resistant kochia(KCHSC-R, Kochia scoparia), Chinese sprangletop (LEFCH, Leptochloachinensis), Italian ryegrass (LOLMU, Lolium multiflorum), wild buckwheat(POLCO, Polygonum convolvulus), giant foxtail (SETFA, Setaria faberi),Johnson grass (SORHA, Sorghum halepense), and wild pansy (VIOTR, Violatricolor) was measured.

The results are summarized in Table 7 below.

TABLE 7 Safening of Effects (% visual injury) of Mefenpyr-diethyl andCompound A on crops and weeds. Appli- Compound 20 0 0 0 20 20 20 cationA 0 20 40 80 20 40 80 rate (g/ha) Mefenpyr- diethyl Herbicide: 1:1 1:21:4 Safener Ratio TRZAW Ob 25 0 0 0 0 0 0 Ex — — — — 25 25 25 Δ −25 −25−25 ORYSA Ob 10 0 0 0 10 0 5 Ex — — — — 10 10 10 Δ 0 −10 −5 ZEAMX Ob 130 0 0 5 10 0 Ex — — — — 13 13 13 Δ −8 −3 −13 ABUTH Ob 95 0 0 0 95 100 97Ex — — — — 95 95 95 Δ 0 5 2 ALOMY Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 00 0 AMARE Ob 93 0 0 0 100 100 100 Ex — — — — 93 93 93 Δ 7 7 7 AVEFA Ob 00 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 BRSNW Ob 85 0 0 0 100 90 100 Ex — —— — 85 85 85 Δ 15 5 15 CHEAL Ob 88 0 0 0 100 100 100 Ex — — — — 88 88 88Δ 12 12 12 CIRAR Ob 95 0 0 0 100 80 85 Ex — — — — 95 95 95 Δ 5 −15 −10CYPES Ob 30 0 0 0 65 30 10 Ex — — — — 30 30 30 Δ 35 0 −20 DIGSA Ob 30 00 0 45 40 35 Ex — — — — 30 30 30 Δ 15 10 5 ECHCG Ob 85 0 0 0 90 80 85 Ex— — — — 85 85 85 Δ 5 −5 0 ERICA Ob 95 0 0 0 95 93 95 Ex — — — — 95 95 95Δ 0 −2 0 GLXMA Ob 100 0 0 0 100 100 100 Ex — — — — 100 100 100 Δ 0 0 0HELAN Ob 95 0 0 0 95 100 100 Ex — — — — 95 95 95 Δ 0 5 5 IPOHE Ob 0 0 00 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0 KCHSC Ob 97 0 0 0 97 95 97 Ex — — — —97 97 97 Δ 0 −2 0 KCHSC- Ob 90 0 0 0 80 85 85 R Ex — — — — 90 90 90 Δ−10 −5 −5 LEFCH Ob 60 0 0 0 30 30 30 Ex — — — — 60 60 60 Δ −30 −30 −30LOLMU Ob 5 0 0 0 5 5 5 Ex — — — — 5 5 5 Δ 0 0 0 POLCO Ob 100 0 0 0 100100 100 Ex — — — — 100 100 100 Δ 0 0 0 SETFA Ob 65 0 0 0 50 65 60 Ex — —— — 65 65 65 Δ −15 0 −5 SORHA Ob 0 0 0 0 0 0 0 Ex — — — — 0 0 0 Δ 0 0 0VIOTR Ob 30 0 0 0 60 60 50 Ex — — — — 30 30 30 Δ 30 30 20 g/ha = gramsper hectare TRZAW = Triticum aestivum (winter wheat) ORYSA = Oryzasativa (common rice) ZEAMX = Zea mays (maize) ABUTH = Abutilontheophrasti (velvetleaf) ALOMY = Alopecurus myosuroides (blackgrass)AMARE = Amaranthus retroflexus (pigweed) AVEFA = Avena fatua (wild oat)BRSNW = Brassica napus (winter rape) CHEAL = Chenopodium album L.(common lambsquarters) CIRAR = Cirsium arvense (Canada thistle) CYPES =Cyperus esculentus (nutsedge) DIGSA = Digitaria sanguinalis (largecrabgrass) ECHCG = Echinochloa crus-galli (barnyardgrass) ERICA =Erigeron canadensis (Canada horseweed) GLXMA = Glycine max (soybean)HELAN = Helianthus annuus (common sunflower) IPOHE = Ipomoea hederacea(ivyleaf morningglory) KCHSC = Kochia scoparia (kochia) KCHSC-R = Kochiascoparia (herbicide-resistant kochia) LEFCH = Leptochloa chinensis(Chinese sprangletop) LOLMU = Lolium multiflorum (Italian ryegrass)POLCO = Polygonum convolvulus (wild buckwheat) SETFA = Setaria faberi(giant foxtail) SORHA = Sorghum halepense (Johnson grass) VIOTR = Violatricolor (wild pansy)

The compositions and methods of the appended claims are not limited inscope by the specific compositions and methods described herein, whichare intended as illustrations of a few aspects of the claims and anycompositions and methods that are functionally equivalent are intendedto fall within the scope of the claims. Various modifications of thecompositions and methods in addition to those shown and described hereinare intended to fall within the scope of the appended claims. Further,while only certain representative compositions and method stepsdisclosed herein are specifically described, other combinations of thecompositions and method steps also are intended to fall within the scopeof the appended claims, even if not specifically recited. Thus, acombination of steps, elements, components, or constituents may beexplicitly mentioned herein; however, other combinations of steps,elements, components, and constituents are included, even though notexplicitly stated. The term “comprising” and variations thereof as usedherein is used synonymously with the term “including” and variationsthereof and are open, non-limiting terms. Although the terms“comprising” and “including” have been used herein to describe variousaspects, the terms “consisting essentially of” and “consisting of” canbe used in place of “comprising” and “including” to provide for morespecific aspects of the invention and are also disclosed. Other than inthe examples, or where otherwise noted, all numbers expressingquantities of ingredients, reaction conditions, and so forth used in thespecification and claims are to be understood to be construed in lightof the number of significant digits and ordinary rounding approaches,and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims.

1. A safened composition, comprising: (a) (a) a pyridine carboxylateherbicide defined by Formula (I):

wherein: R¹ is cyanomethyl or propargyl; R² and R^(2′) are independentlyhydrogen, C₁-C₆ alkyl, formyl, alkoxycarbonyl, or acyl; R³, R^(3′),R^(3″), and R^(3′″) are independently hydrogen, halogen, C₁-C₄ alkyl,C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy; or an agriculturallyacceptable N-oxide, salt, or ester thereof; and (b) an azole carboxylatesafener or an agriculturally acceptable salt or ester thereof.
 2. Thecomposition of claim 1, wherein the pyridine carboxylate herbicidecompound is cyanomethyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


3. The composition of claim 1, wherein the pyridine carboxylateherbicide compound is propargyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


4. The composition of claim 1, wherein the azole carboxylate safener isselected from the group consisting of fenchlorazole, flurazole,furilazole, isoxadifen, mefenpyr, an agriculturally acceptable salt orester thereof, and mixtures thereof.
 5. The composition of claim 4,wherein the agriculturally acceptable ester of the azole carboxylatesafener is selected from the group consisting of methyl ester, ethylester, diethyl ester, and combinations thereof.
 6. The composition ofclaim 4, wherein the agriculturally acceptable salt of the azolecarboxylate safener is selected from the group consisting of sodium,potassium, ammonium, monoethanolammonium, diethanolammonium,triethanolammonium, monoisopropanolammonium, diisopropanolammonium,triisopropanolammonium, choline, N,N-dimethylethanolammonium,diethylammonium, dimethylammonium, trimethylammonium, triethylammonium,isopropylammonium salts, and combinations thereof.
 7. The composition ofclaim 1, wherein the weight ratio of the pyridine carboxylate herbicide(in g ae/ha) to the azole carboxylate safener (in g ai/ha) is from about1:5 to about 5:1.
 8. The composition of claim 1, further comprising anadditional pesticide.
 9. The composition of claim 1, wherein thecomposition does not include a herbicidal active ingredient in additionto (a).
 10. A method of controlling undesirable vegetation, comprisingapplying to vegetation or an area adjacent the vegetation or applying tosoil or water to limit the emergence or growth of vegetation a safenedcomposition, comprising: (a) (a) a pyridine carboxylate herbicidedefined by Formula (I):

wherein R¹ is cyanomethyl or propargyl; R² and R^(2′) are independentlyhydrogen, C₁-C₆ alkyl, formyl, alkoxycarbonyl, or acyl; R³, R^(3′),R^(3″), and R^(3′″) are independently hydrogen, halogen, C₁-C₄ alkyl,C₁-C₄ haloalkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkoxy; or an agriculturallyacceptable N-oxide, salt, or ester thereof; and (b) an azole carboxylatesafener or an agriculturally acceptable salt or ester thereof; whereinthe herbicide is applied in an amount of at least 1 g ae/ha; and whereinthe azole carboxylate safener is applied in an amount of at least 1 gai/ha.
 11. The method of claim 10, wherein the pyridine carboxylateherbicide compound is cyanomethyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


12. The method of claim 10, wherein the pyridine carboxylate herbicidecompound is propargyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate:


13. The method of claim 10, wherein the herbicide and the safener areapplied simultaneously.
 14. The method of claim 10, wherein the azolecarboxylate safener is selected from the group consisting offenchlorazole, flurazole, furilazole, isoxadifen, mefenpyr, anagriculturally acceptable salt or ester thereof, and mixtures thereof.15. The method of claim 14, wherein the agriculturally acceptable esterof the azole carboxylate safener is selected from the group consistingof methyl ester, ethyl ester, diethyl ester, and combinations thereof.16. The method of claim 14, wherein the agriculturally acceptable saltof the azole carboxylate safener is selected from the group consistingof sodium, potassium, ammonium, monoethanolammonium, diethanolammonium,triethanolammonium, monoisopropanolammonium, diisopropanolammonium,triisopropanolammonium, choline, N,N-dimethylethanolammonium,diethylammonium, dimethylammonium, trimethylammonium, triethylammonium,isopropylammonium salts, and combinations thereof.
 17. The method ofclaim 10, wherein the herbicide is provided in amount of 1 g ae/ha to300 g ae/ha.
 18. The method of claim 10, wherein the pyridinecarboxylate herbicide is applied pre-emergently or post-emergently tothe undesirable vegetation and the azole carboxylate safener is appliedas a seed treatment to the crop.
 19. The method of claim 10, whereinweight ratio of the pyridine carboxylate herbicide (in g ae/ha) to theazole carboxylate safener (in g ai/ha) is from about 1:5 to about 5:1.20. The method of claim 10, further comprising applying an additionalpesticide.
 21. The method of claim 10, wherein the composition does notinclude a herbicidal active ingredient in addition to (a).